CN103443234B - Fire retardant adhesive - Google Patents

Abstract

The invention discloses the contact adhesive with flame-retarding characteristic, it comprises (methyl) acrylate group block copolymer and the halogen-free flame-retardant of at least 10 weight %.Described binding agent can comprise extra optional additives, such as tackifying resin, plasticizer etc..Described binding agent prepares by carrying out being blended by described (methyl) acrylate group block copolymer and described halogen-free flame-retardant in solvent process or solvent-free process.

Description

Fire retardant adhesive

Technical field

Present invention relates generally to binding agent and adhesive tape area, in particular relate to the contact adhesive with flame-retardant properties And adhesive tape area.

Background technology

Binding agent has been used for various labelling, fixes, protects, seal and shelter purposes.Adhesive tape generally includes backing (also referred to as Base material) and binding agent.One class binding agent, i.e. contact adhesive, is useful especially for many application.

Contact adhesive is known to those skilled in the art, and it at room temperature has some characteristic, these Characteristic includes following item: the adhesion strength that (1) is strong and lasting；(2) can adhere to the pressure less than finger pressure；(3) there is foot Enough it is fixed on the ability on adherend；And (4) enough cohesive strength is to make it be cleanly removed from adherend.Send out Existing, polymer, as pressure sensitive adhesive material function admirable, can be designed and formulated and have required viscoelasticity, so that viscous The property, peel adhesion and shear strength reach required balance.Prepare the most frequently used polymer of contact adhesive have natural rubber, Synthetic rubber (e.g., styrene/butadiene copolymers (SBR) and styrene/isoprene/styrene (SIS) block copolymer), Various (methyl) acrylate (e.g., acrylate and methacrylate) copolymer and organosilicon.The material of these types is each There is merits and demerits.

One class pressure-sensitive adhesive polymers material is (methyl) acrylate block copolymer.These polymer comprise arrangement Acrylate in block and/or methacrylate polymers segment.The preparation method of these polymer and by them The pressure-sensitive adhesive article made is at United States Patent (USP) No.6,806,320 (Everaerts et al.), No.6,734,256 (Everaerts et al.), No.7,084,209 (Everaerts et al.) and No.7,255,920 (Everaerts et al.) and PCT Publication No.WO2009/146227 (Joseph et al.) and No.WO2009/111433 (Tse et al.) is described.

In material, with the addition of flame-retardant additive to improve the fire resistance of these materials.It is added to fire-retardant The material of additive has: the thermoplastic resin composition in United States Patent (USP) No.5,952,408 (Lee et al.)；United States Patent (USP) No.4, the resin in 526,917 (Axelrod), the yarn fabric in Japan Patent No.JP2006045418 (Hamada et al.) and Wire coating；And the high impact poly carbonic ester molding compounds in United States Patent (USP) No.5,061,745 (Wittmann et al.). It addition, adhesive stroma is prepared fire retardant adhesive and contact adhesive by being added to by flame-retardant additive.These glue The example of mixture includes: U.S. Patent Publication No.2007/0059521 (Nakamura), it relates in acrylic polymer Use hydrated metal compound；United States Patent (USP) No.5,851,663 (Parson et al.), it relates to non-halogen expansion type flame-retarding pressure Sensitive adhesive and adhesive tape；U.S. Patent Publication 2009/0291291 (Epple), it relates to a kind of flame-retardant pressure-sensitive binding agent, this resistance Combustion contact adhesive comprises metal-oxide, metal hydrate, halogenated materials and liquid phosphorus tribromide；United States Patent (USP) No.6, 114,426 (Burack et al.), it relates to a kind of fire retardant adhesive, and this fire retardant adhesive comprises acrylic polymer, dibromo Styrene and vinyl phosphoric acid；And U.S. Patent Publication No.2010/0009181 (Umemoto et al.), it relates to one not Halogen-containing pressure-sensitive adhesive tape, this pressure-sensitive adhesive tape comprises the acrylic resin of modification and the bonding obtained by non-halogenated resin-made Tape backing.

Summary of the invention

The binding agent being to have flame-retarding characteristic disclosed herein, especially contact adhesive, and preparation have fire-retardant The method of the binding agent of characteristic.This binding agent comprises (methyl) acrylate group block copolymer, and at least 10 weight % Halogen-free flame-retardant.This binding agent is flame-retardant pressure-sensitive binding agent.This binding agent can comprise extra optional additives, such as, viscosify Resin, plasticizer etc..

The invention also discloses the method that preparation has the binding agent of flame-retarding characteristic.These methods include providing (methyl) third Olefin(e) acid ester group block copolymer, offer halogen-free flame-retardant, and by (methyl) acrylate group block copolymer and halogen-free resistance Combustion agent is blended to form contact adhesive.Halogen-free flame-retardant accounts at least 10 weight % of binding agent.By (methyl) acrylate Group block copolymer is blended with halogen-free flame-retardant and solvent-borne type technique or solvent-free process can be used to complete.

Detailed description of the invention

The use of binding agent especially contact adhesive is the most increasingly extensive.The use of binding agent field the most widely includes doctor Learn, electronics and optics industry and consumer goods and public transport.These industries need binding agent to have special nature.Such as, need Binding agent (such as contact adhesive) is wanted to have the special nature being better than traditional viscosity, peel adhesion and shear strength.For Meet the performance requirement day by day harsh to binding agent, need all kinds of new material.In various performance requirements, including optical clarity Degree and anti-flammability.Generally the optical clarity of binding agent had requirement, because adhesive phase is typically optical goods or device Parts；And require that binding agent has anti-flammability, with suppression or slow down spreading thus protecting personnel and property safety of the intensity of a fire.

Multiple technologies can be used to prepare fire retardant adhesive.In binding agent, generally add flame-retardant additive so that binding agent There is flame-retarding characteristic.Many commonly-used flame-retardant additive comprises halogen, such as Polychlorinated biphenyls and PBDE.But, people Have become increasingly aware of halogen containing material to environmentally undesirable, therefore the use in binding agent of these materials is just being increasingly subject to limit System.It addition, the optical property of binding agent may be adversely affected by the use of flame-retardant additive.

Disclosed herein is binding agent (such as contact adhesive), and this binding agent is except having binding agent required property normally Beyond matter (peel strength, shearing retentivity and cohesiveness), also there is multiple ideal characterisitics.This binding agent has flame-retarding characteristic, And in certain embodiments or optical clarity.This flame-retarding characteristic just can obtain without using halogen-containing flame-retardant additive ?.Resistance is realized by selecting elastomer polymer ((methyl) acrylate group block copolymer) and use halogen-free flame-retardant Combustion characteristic and the combination of optical clarity.

Except as otherwise noted, otherwise all expression characteristic sizes, amount and thing used in specification and claims The numerical value of reason characteristic all should be understood to be modified by term " about ".Therefore, unless indicated to the contrary, otherwise in description above and The numerical parameter listed in appended claims is approximation, and these approximations can make according to those skilled in the art Seek the desirable properties of acquisition by teachings disclosed herein and change.Include being included into this with the numerical range of end points statement In the range of all numerical value (e.g., 1 to 5 include 1,1.5,2,2.75,3,3.80,4 and 5) and should in the range of any scope.

As used in the present specification, and in the appended claims, all of non-complex form contains and has multiple thing that refers to Embodiment, unless this content additionally explicitly points out.Such as, mention that " one layer " can contain the enforcement with one layer, two-layer or multilamellar Example.As used in this specification and attached claims, term "or" typically makes with the meaning comprising "and/or" With, unless in have and additionally clearly state.

As used herein, term " binding agent " refers to the polymer composition that can be used for being adhered to each other by two adherends. The example of binding agent is contact adhesive.

Those skilled in the art know, and contact adhesive composition has the spy including following characteristic Property: the adhesion strength that (1) is strong and lasting；(2) can adhere to the pressure less than finger pressure；(3) have and be enough fixed on bonding Ability on body；And (4) enough cohesive strength is to make it be cleanly removed from adherend.Have been found that and be suitable for use as pressure The material of sensitive adhesive is such polymer, and it is through design and prepares to show required viscoelasticity, causes cohesiveness, stripping From balance required between bonding force and shearing retentivity.Obtaining suitable balance of properties is not a simple process.

Term " containing halogen " or " without halogen " refer to material, particularly adhesive additive.The most halogen-containing interpolation Agent is substantially free of halogen atom, such as fluorine, chlorine, bromine and atomic iodine.At least some hydrogen atom quilts in halogen-containing additive Halogen atom replaces.

Except as otherwise noted, otherwise " optical clear " refers to goods, film or binding agent (about 400nm is to about in visible light On 700nm) at least some of, there is high transmission rate.Term " transparent membrane " refers to have certain thickness and when being arranged on base material The thin film of image (being arranged on base material or near base material) can be seen through the thickness of this transparent membrane time upper.In many embodiments In, transparent membrane allows the thickness passing through film in the case of inconspicuous loss image definition to see image.Implement at some In example, transparent membrane surface has matte management or upper optical processing.

Except as otherwise noted, otherwise " optical clarity " refers at least in visible light (about 400nm to about 700nm) There is on Fen high transmission rate and present binding agent or the goods of low haze.

Term " (methyl) acrylate " refers to monomeric acrylic or the methacrylate of alcohol.Acrylate and methyl-prop Alkene acid ester monomer or oligomer are collectively referred to herein as " (methyl) esters of acrylic acid ".When being used for describing polymer (such as block Copolymer) time, term " (methyl) is acrylate-based " refers to the polymer prepared by (methyl) acrylate monomer.These polymerizations Thing can only comprise (methyl) acrylate monomer, or they can comprise the list with (methyl) esters of acrylic acid coreaction Body.

As used herein, term " polymer " " refer to the polymeric material for homopolymer or copolymer.As used herein, term " homopolymer " refers to the polymeric material of the product for a kind of monomer.As used herein, term " copolymer " refers to be at least two Plant the polymeric material of the product of different monomers.As used herein, term " block copolymer " refers to pass through at least two The mutual covalent bonding of different polymer blocks and the copolymer that formed.It is embedding that the polymer blocks that the two is different is referred to as A Section and B block.Typically, A block by between A block and B block be separated and formed by the B block that rigidity is more weak Dominant continuous phase in discontinuous enhancing " nanometer territory " is provided, strengthen elastomer with cohesion.Term used herein " it is separated " and refers in the matrix comprising softer B block phase, there is distinguishing enhancing A block domains (that is, nanometer territory).For Presenting optical clarity, separated nanometer territory should be less than the wavelength (about 400 to about 700nm) of visible ray.

Term " tackifying resin " and " viscosifier " are used interchangeably in this article.

Term " resin of plastification " and " plasticizer " are used interchangeably in this article.

Term " alkyl " refers to the univalent perssad of alkane, and described alkane is saturated hydrocarbons.Alkyl can be straight chain, side chain, Ring-type or combinations thereof, and it is generally of 1 to 20 carbon atom.In certain embodiments, alkyl contain 1 to 18,1 To 12,1 to 10,1 to 8,1 to 6 or 1 to 4 carbon atom.The example of alkyl group include, but is not limited to methyl, Ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, second Base hexyl, positive lauryl, isodecyl, tridecyl, myristyl, cetyl and octadecyl.

Term " aryl " refers to aromatics and carbocyclic ring univalent perssad.Aryl can have one to five and be connected with aromatic ring or thick The ring closed.Other ring structures can be aromatics, non-aromatic or combinations thereof.The example of aromatic yl group includes (but not limiting In) phenyl, xenyl, terphenyl, anthryl (anthryl), naphthyl, acenaphthenyl, anthraquinonyl, phenanthryl, anthryl (anthracenyl), pyrenyl, base and fluorenyl.

Term " alkylidene " refers to as the divalent group into alkane group.Alkylidene can be straight chain, side chain, ring-type Or combinations thereof.Alkylidene often has 1 to 20 carbon atom.In certain embodiments, alkylidene comprise 1 to 18,1 to 12,1 to 10,1 to 8,1 to 6 or 1 to 4 carbon atom.The radical center of alkylidene can at same carbon atom (i.e. Alkylidene radical) go up or on different carbon atom.

Term " miscellaneous alkyl " refers to comprise the monoradical of at least two alkylidene group, said two alkylidene group warp Being connected by sulfur, oxygen or-NR-, wherein R is alkyl.Miscellaneous alkyl can be straight chain, side chain, ring-type, alkyl group is substituted Or combinations thereof.Some miscellaneous alkyl is polyoxyalkylene, and wherein hetero atom is oxygen, such as CH₃CH₂(OCH₂CH₂)_nOCH₂CH₂-。

Term " arlydene " refers to carbocyclic ring and aromatics divalent group.This group has 1 to 5 and is connected, condenses or it The ring of combination.Other rings can be aromatics, non-aromatic or combinations thereof.In certain embodiments, arlydene base Group has up to 5 rings, up to 4 rings, up to 3 rings, up to 2 rings or 1 aromatic ring.Such as, arlydene base Group can be phenylene.

Term " heteroarylidene " refers to carbocyclic ring and aromatics divalent group, and it comprises hetero atom such as sulfur, oxygen, nitrogen or halogen (such as fluorine, chlorine, bromine or iodine).

Term " aralkyl " refers to formula R^a-Ar^aMonoradical, wherein R^aFor alkylidene and Ar^a(that is, sub-for aryl Alkyl is bonded with aryl).

Term " free redical polymerization " and " ethylenic is undersaturated " are used interchangeably, and refer to comprise can be by freely The reactive group of the carbon-to-carbon double bond of base flowcollector aggregation scheme FlowCollector polymerization.

Disclosed herein is binding agent.This binding agent typically comprises layer, and usually pantostrat.Adhesive phase can be Independent stratum, such as transfering belt；Or binding agent can be coated on backing or base material form adhesive article.

The binding agent of the present invention comprises the halogen-free of (methyl) acrylate group block copolymer and at least 10 weight % Fire retardant.This binding agent is flame-retardant pressure-sensitive binding agent.In certain embodiments, binding agent can also be optical clear or optics clear Clear.

Pressure sensitive adhesive layer comprises (methyl) acrylate group block copolymer, and this copolymer comprises at least two A block Polymer unit and product (that is, at least two A block polymer unit covalency of at least one B block polymer unit Be bonded at least one B block polymer unit).The Tg of each A block is at least 50 DEG C, and it is the first monomer composition Product, described first monomer composition comprises alkyl methacrylate, methacrylic acid aralkyl ester, metering system Acid aryl ester or combinations thereof.The Tg of B block is not more than 20 DEG C, and it is the product of second comonomer compositions, and described Two monomer compositions comprise (methyl) alkyl acrylate, the miscellaneous Arrcostab of (methyl) acrylic acid, vinyl esters or combinations thereof. Block copolymer comprises A block and the B block of 50 to 80 weight % of weight meter 20 to 50 weight % based on block copolymer.

The method using active anionic polymerization method to prepare block copolymer is further described in (such as) United States Patent (USP) No.6,734,256 (Everaerts et al.), No.7,084,209 (Everaerts et al.), No.6,806,320 (Everaerts et al.) and No.7,255,920 (Everaerts et al.).This polymerization is further described in (such as) U.S. Patent No.6,630,554 (Hamada et al.) and No.6,984,114 (Kato et al.) and Japanese patent application Kokai are open The most flat 11-302617 (Uchiumi et al.) and the flat 11-323072 of No. (Uchiumi et al.).Suitably block copolymer is permissible Kuraray Co., Ltd (Kuraray Co., the LTD. of Tokyo it is purchased from trade name LAPOLYMER or KURARITY (Tokyo, Japan)).Some (such as LA2140E, LA2250, LA2330 and LA410L) in these block copolymers are tool There are poly-(methyl methacrylate) end-blocks and the triblock copolymer of poly-(n-butyl acrylate) mid-block.United States Patent (USP) No.7, the block copolymer described in 255,920 (Everaerts et al.) is particularly suitable, because these block copolymers are light Learn clearly.

Block copolymer in pressure sensitive adhesive layer can be triblock copolymer (that is, (A-B-A) structure) or star embedding Section copolymer (that is, (A-B)_n-structure, wherein n is the integer of at least 3).There is the central point that a plurality of side chain extends out from it Star block copolymer be also referred to as radial copolymers.

Each A block polymer unit and each B block polymer unit can be homopolymer or copolymer.A block Usually end-blocks (that is, the end of A block formation copolymer material), and B block is usually mid-block (that is, B block Form the mid portion of copolymer material).A block is usually hard block, and it is thermoplastic；And B block is usually soft embedding Section, it is elastomeric material.

As used herein, term " thermoplasticity " refers to flow when heated, and return it when being cooled back to room temperature initial The polymeric material of state.As used herein, term " elastomer " refers to be stretchable at least twice of its initial length, then The polymeric material of about its initial length it is contracted to when release.

A block often has higher rigidity (that is, the glass transition temperature of A block is higher than B block) than B block.As Used herein, term " glass transition temperature " or " Tg " refer to polymeric material by glassy state (e.g., enbrittle, hardness and Rigidity) temperature when being converted to rubbery state (e.g., there is pliability and elasticity).Tg may utilize (such as) differential scanning calorimetry Or dynamic mechanical analysis (DMA) technology measures (DSC).The Tg of A block is at least 50 DEG C, and the Tg of B block is not higher than 20 DEG C. A block is often that (methyl) acrylate block copolymer provides structural strength and cohesive strength.

Block copolymer typically at least has orderly many phase morphologies within the temperature range of about 25 DEG C to about 150 DEG C.Cause Solubility parameter for A block is the most different from B block, so A block phase is mutually typically separate with B block.Block copolymerization Thing can have the zones of different adding epistasis A block domains (e.g., nanometer territory) in the substrate of softer elastomeric B block.That is, block Copolymer generally substantially continuous B block mutually in there is discrete discontinuous A block phase.

Each A block is the product of the first monomer mixture, and this first monomer mixture comprises at least one Formulas I Methacrylate monomer:

H₂C=C(CH₃)-(CO)-OR¹

Formulas I

Wherein R¹For alkyl (that is, can be alkyl methacrylate according to the monomer of Formulas I), aralkyl (that is, according to formula The monomer of I can be methacrylic acid aralkyl ester) or aromatic yl group (that is, according to the monomer of Formulas I can be methacrylic acid virtue Base ester).Suitably alkyl group is generally of 1 to 6 carbon atom.When alkyl group has more than 2 carbon atoms, alkyl base Group can be side chain or ring-type.Suitably aromatic alkyl group (that is, aralkyl is the alkyl group replaced by aromatic yl group) leads to Often there are 7 to 12 carbon atoms, and suitably aromatic yl group is generally of 6 to 12 carbon atoms.

Exemplary monomer according to Formulas I includes methyl methacrylate, ethyl methacrylate, methacrylic acid isopropyl Ester, isobutyl methacrylate, Tert-butyl Methacrylate, cyclohexyl methacrylate, phenyl methacrylate and methyl-prop Olefin(e) acid benzyl ester.

In addition to the monomer of Formulas I, A block can comprise the polar monomer of up to 10 weight %, such as (methyl) acrylic acid, (methyl) acrylamide or (methyl) acrylic acid hydroxy alkyl ester.These polar monomers may be used for the Tg of (such as) regulation A block (nonetheless Tg remains as at least 50 DEG C) and cohesive strength.It addition, if it is required, these polar monomers can play chemical crosslinking Or the effect of the reactive site of ionomer.

As used herein, term " (methyl) acrylic acid " refers to acrylic acid and methacrylic acid.As used herein, art Language " (methyl) acrylamide " refers to acrylamide and Methacrylamide.(methyl) acrylamide can be N-alkyl (methyl) acrylamide or N, N-dialkyl group (methyl) acrylamide, wherein alkyl substituent has 1 to 10,1 to 6 or 1 to 4 Carbon atom.Exemplary (methyl) acrylamide includes acrylamide, Methacrylamide, N methacrylamide, N-methyl first Base acrylamide, N,N-DMAA, N, N-dimethylmethacryl amide and N-octyl group acrylic amine.

As used herein, term " (methyl) acrylic acid hydroxy alkyl ester " refers to acrylic acid hydroxy alkyl ester or hydroxyethyl methacrylate Arrcostab, wherein the substituted alkyl group of hydroxyl has 1 to 10,1 to 6 or 1 to 4 carbon atom.Exemplary (methyl) acrylic acid Hydroxyalkyl esters includes acrylic acid 2-hydroxyl ethyl ester, HEMA, acrylic acid 3-hydroxypropyl acrylate and methacrylic acid 3- Hydroxypropyl acrylate.

A block in block copolymer can be identical or different.In certain block copolymers, each A block is Poly-(methyl methacrylate).In more specifically example, block copolymer can be triblock copolymer or starblock altogether Polymers, the most each end-blocks is poly-(methyl methacrylate).

The weight average molecular weight (Mw) of each A block generally at least about 5,000 grams/mol.In certain block copolymers, The weight average molecular weight of A block is at least about 8,000 grams/mol or at least about 10,000 grams/mol.The weight average molecular weight of A block Generally less than about 30,000 grams/mol or less than about 20,000 grams/mol.The weight average molecular weight of A block can be (such as) about 5,000 to about 30,000 grams/mol, about 10,000 to about 30,000 grams/mol, about 5,000 to about 20,000 grams/mol or about 10,000 to about 20,000 grams/mol.

The Tg of each A block is at least 50 DEG C.In certain embodiments, the Tg of A block be at least 60 DEG C, at least 80 DEG C, At least 100 DEG C or at least 120 DEG C.Tg is usually more than 200 DEG C, is not more than 190 DEG C or no more than 180 DEG C.Such as, A block Tg can be 50 DEG C to 200 DEG C, 60 DEG C to 200 DEG C, 80 DEG C to 200 DEG C, 100 DEG C to 200 DEG C, 80 DEG C to 180 DEG C or 100 DEG C extremely 180℃。

B block is the product of second comonomer compositions, and this second comonomer compositions comprises (methyl) acrylic acid alkyl Ester, the miscellaneous Arrcostab of (methyl) acrylic acid, vinyl esters or combinations thereof.As used herein, term " (methyl) acrylic acid alkyl Ester " refer to alkyl acrylate or alkyl methacrylate.As used herein, term " the miscellaneous Arrcostab of (methyl) acrylic acid " is Referring to the miscellaneous Arrcostab of acrylic acid or the miscellaneous Arrcostab of methacrylic acid, the most miscellaneous alkyl has at least two carbon atom and at least one chain Middle hetero atom (e.g., sulfur or oxygen).

Exemplary vinyl esters includes, but is not limited to vinyl-acetic ester, 2 ethyl hexanoic acid vinyl esters and neodecanoic acid Vinyl acetate.

Exemplary (methyl) alkyl acrylate and the miscellaneous Arrcostab of (methyl) acrylic acid are generally of Formula II

H₂C=CR²-(CO)-OR³

Formula II

Wherein R²For hydrogen or methyl；And R³For C_3-18Alkyl or C_2-18Miscellaneous alkyl.Work as R²For during hydrogen (that is, according to Formula II Monomer is acrylate), R³Group can be straight chain, side chain, ring-type or combinations thereof.Work as R²For methyl (that is, root It is methacrylate according to the monomer of Formula II) and R³When there is 3 or 4 carbon atoms, R³Group can be straight chain.Work as R²For Methyl and R³When there is at least 5 carbon atoms, R³Group can be straight chain, side chain, ring-type or combinations thereof.

Suitable monomer according to Formula II includes, but is not limited to n-butyl acrylate, decyl acrylate, acrylic acid 2-second Epoxide ethyl ester, methacrylic acid 2-ethoxy ethyl ester, isoamyl acrylate, the most own ester of acrylic acid, the most own ester of methacrylic acid, third Olefin(e) acid isobutyl ester, isodecyl acrylate, isodecyl methacrylate, acrylic acid different nonyl ester, 2-EHA, methyl-prop Olefin(e) acid 2-Octyl Nitrite, Isooctyl acrylate monomer, 2-Propenoic acid, 2-methyl-, isooctyl ester, acrylic acid isotridecyl ester, lauryl acrylate, Lauryl methacrylate, acrylic acid 2-methoxy acrylate, acrylic acid 2-methylbutyl butenoate, acrylic acid 4-methyl-2-amyl group ester, third Olefin(e) acid n-octyl, n-propyl, n octyl methacrylate, aliphatic acrylate, acrylic acid myristyl ester and Octadecyl acrylate.

The most commercially available or can not be prepared by the monomer according to Formula II (methyl) arylate blocks of direct polymerization, institute State block to be provided by esterification or ester exchange reaction.Such as, can be by commercially available (methyl) acrylate hydrolysis, then Carry out with alcohol being esterified (methyl) acrylate paid close attention to offer.This process may leave some residual acid in B block. Or, by the direct ester exchange reaction of (methyl) lower alkyl acrylate Yu senior alkyl alcohol, can be from (methyl) acrylic acid Lower alkyl esters is derivative obtains (methyl) acrylic acid higher alkyl esters.

On the premise of the Tg of B block is not more than 20 DEG C, B block can comprise the polar monomer of up to 30 weight %.Pole Property monomer includes, but is not limited to (methyl) acrylic acid；(methyl) acrylamide, such as N-alkyl (methyl) acrylamide and N, N-dialkyl group (methyl) acrylamide；(methyl) acrylic acid hydroxy alkyl ester；And N-vinyl lactam, such as N-vinylpyridine Pyrrolidone and N-caprolactam.Polar monomer can be included in Tg or the cohesive strength in B block with regulation B block.Separately Outward, if it is desired, polar monomer can play the effect of the reactive site of chemical crosslinking or ionomer.

The Tg of B block is usually more than 20 DEG C.In certain embodiments, the Tg of B block be not more than 10 DEG C, be not more than 0 DEG C, It is not more than-5 DEG C or is not more than-10 DEG C.Tg is usually not less than-80 DEG C, not less than-70 DEG C or not less than-50 DEG C.Such as, B block Tg can be-70 DEG C to 20 DEG C ,-60 DEG C to 20 DEG C ,-70 DEG C to 10 DEG C ,-60 DEG C to 10 DEG C ,-70 DEG C to 0 DEG C ,-60 DEG C to 0 DEG C ,-70 DEG C to-10 DEG C or 60 DEG C to-10 DEG C.

B block is often elastomer.As used herein, term " elastomer " refers to be stretchable to its initial length at least Twice, is then contracted to the polymeric material of about its initial length when release.In some contact adhesive compositions, add Add extra elastomeric material.The elastomeric material added should be to the optical clarity of contact adhesive composition or bonding Agent character (e.g., storage modulus) has a negative impact.(e.g., the chemical property of B block may affect the cohesiveness of block copolymer The block copolymer with relatively low rubber platform storage modulus (as used dynamic mechanical analysis method to determine) is the most viscous).

In certain embodiments, be (methyl) alkyl acrylate according to the monomer of Formula II, wherein alkyl group have 4 to 18,4 to 10,4 to 6 or 4 carbon atoms.In some instances, monomer is acrylate.Acrylate monomer often than they Methacrylate counter pair has lower rigidity.Such as, B block can be poly-(n-butyl acrylate).

The weight average molecular weight of B block generally at least about 30,000 grams/mol.In certain block copolymers, B block Weight average molecular weight is at least about 40,000 grams/mol or at least about 50,000 grams/mol.Weight average molecular weight is generally no greater than about 200,000 grams/mol.The weight average molecular weight of B block usually more than 150,000 grams/mol, no more than about 100,000 grams/rub You or no more than about 80,000 grams/mol.In certain block copolymers, the weight average molecular weight of B block is about 30,000 gram/rub You are to about 200,000 grams/mol, about 30,000 grams/mol to about 100,000 grams/mol, about 30,000 grams/mol to about 80, 000 gram/mol, about 40,000 grams/mol to about 200,000 grams/mol, about 40,000 grams/mol to about 100,000 grams/rub You or about 40,000 grams/mol to about 80,000 grams/mol.

B block is the polymeric material as homopolymer, and its average entanglement molecular weight is not greater than about 60,000 gram/mol. As used herein, term " average entanglement molecular weight " is the average distance between the entanglement in the random coil of polymeric material Index, and refer to the mean molecule quantity between tangling.If the weight average molecular weight of B block is more than average entanglement molecular weight, then B is embedding Section polymer will tangle.In some B block, average entanglement molecular weight is not greater than about 50,000 gram/mol or be not more than About 40,000 grams/mol.Entanglement molecular weight can change by selecting the monomer being used for preparing B block.Such as, poly-(acrylic acid N-butyl) entanglement molecular weight the most poly-(Isooctyl acrylate monomer).

Block copolymer usually contains A block and 50 to 80 weights of weight meter 20 to 50 weight % based on block copolymer The B block of amount %.Such as, copolymer can containing the A block of 20 to 40 weight % and the B block of 60 to 80 weight %, 25 to 40 The A block of weight % and the B block of 60 to 75 weight %, the A block of 30 to 40 weight % and the B block of 60 to 70 weight %, The A block of 20 to 35 weight % and the B block of 65 to 80 weight %, the A block of 25 to 35 weight % and the B of 65 to 75 weight % Block, or the A block of 30 to 35 weight % and the B block of 65 to 70 weight %.Higher A block concentration often increases copolymer Cohesive strength.If the too high levels of A block, then the cohesiveness of block copolymer low may obtain and cannot accept.It addition, such as The really too high levels of A block, then the form of block copolymer may be sent out from desired structure (now B block formation continuous phase) Raw reversing, is changed into and is formed continuous phase by A block, and block copolymer will have a characteristic of thermoplastic and non-sensitive glue Mixture properties of materials.

Block copolymer has saturated main polymer chain.Therefore, these polymeric materials tend to resistance to climate and draw (that e.g., ultraviolet radiation cause or caused by the oxidation) degraded risen.Even if still further, it was discovered that these polymer are not being deposited In the case of flame-retardant additive, himself also has a certain degree of flame-retarding characteristic.Such as, it has been observed that to there is similar point Son is measured but is not that block copolymer (methyl) acrylate polymer is compared, and (methyl) acrylate block copolymer has low Specific heat release, thus provide fire retardant characteristic.

Any technology for producing the good block controlled and block copolymer structure can be used in preparing this block altogether Polymers.As used herein, term " good control " refers to that block or block copolymer structure have in following properties at least One: molecular weight is controlled, polydispersity is low, block defines well (well-defined), or block has high-purity.

Some blocks and block copolymer have the molecular weight of good control.That is, when synthesizing A block and B block, it is thus achieved that The molecular weight close with theoretical molecular.As used herein, term " theoretical molecular " refers to based on for forming each block Monomer and the calculating molecular weight of mole of feed (molar charge) of initiator.For living polymer, term " polymerization journey Degree " or " DP " refer to the number of monomeric repeating unit in representative polymer backbones.The molal quantity of DP monomer available is divided by initiator Molal quantity calculate.Theoretical molecular is multiplied by the formula weight of the monomeric unit for preparing block homopolymer equal to DP, or is equal to DP is multiplied by the average formula weight of the monomeric unit for preparing block copolymer.Weight average molecular weight (Mw) is usually theoretical molecular About 0.8 to about 1.2 times, or be about 0.9 to about 1.1 times of theoretical molecular.Therefore, it can prepare and there is selected molecular weight Block and block copolymer.

Block and block copolymer are generally of low polydispersity.As used herein, term " polydispersity " is molecule Measuring of amount distribution, refers to the weight average molecular weight (Mw) number-average molecular weight (Mn) divided by polymer of polymer.It is respectively provided with identical The polydispersity of the material of molecular weight is 1.0, and has the polydispersity of the material of more than one molecular weight more than 1.0.Many points Scattered property can such as determine with gel permeation chromatography.Some blocks and block copolymer have 2.0 or less, 1.5 or less or The polydispersity of person 1.2 or less.

In certain block copolymers, comprise the boundary between nanometer territory and the continuous phase comprising B block of A block clear and definite (that is, border is substantially free of grading structure-derived from the structure of the monomer for A block and B block).Grading structure can Increase A block phase and the mixing of B block phase, thus cause total cohesive strength of contact adhesive to reduce.

Some A blocks and B block have high-purity.Such as, during A block can be substantially free of derived from preparation B block The segment of monomer used.Similarly, B block can be substantially free of the segment derived from monomer used during preparing A block.

In general, polymerization does not use iniferter.Iniferter can leave residue, These residues especially can throw into question in light-initiated polyreaction.Such as, thiocarbamate (a kind of conventional drawing Send out-transfer-terminator) existence gained block copolymer may be caused to be more susceptible to the impact of degraded that weather causes.It is believed that by The degraded that weather causes is probably caused by carbon relatively weak in thiocarbamate residue-sulfur connects.Sulfur is for ammonia The existence of carbamate can such as use elementary analysis or mass spectrography to detect.

It is often used for preparing the good block of control and the technology of block copolymer structure can include active free radical polymerization Technology, active anionic polymerization technology and group transfer polymerization technology.The object lesson of living free radical polymerization includes former The reaction of sub-transfer polymerization and reversible addion-fragmentation chain transfer polyreaction.

As used herein, term " living polymerization " refers to that the material wherein expanded does not occurs to terminate or the polymerization skill of transfer Art, process or reaction.If adding extra monomer after 100% converts, then can occur further to be polymerized.Because amplification The invariable number of material, thus the molecular weight of living polymer with convert carry out and linear increase.This type of polymerization generally may be used For preparing block copolymer.

Activity polymerizating technology generally yields than uses nonactive or pseudo-activity polymerizating technology and (such as uses initiation-transfer-end The only polyreaction of agent) the prepared more stereoregulated block structure of block.Steric regularity (by height syndiotactic structure or Isotactic structure proves) often lead to the block structure that well controls, and often affect the glass transition temperature of block.Example As, use the syndiotaxy poly-(methyl methacrylate) (PMMA) of activity polymerizating technology synthesis can have ratio and use routine (i.e. Nonactive) glass transition temperature of high about 20 DEG C to about 25 DEG C of similar PMMA of polymerization technique synthesis.Steric regularity can example As used nuclear magnetic resonance spectroscopy to detect.The structure of the steric regularity with greater than about 75% generally can use living polymerization skill Art obtains.

When activity polymerizating technology is used for being formed block, monomer can be made to contact with initiator in the presence of inert diluent. Inert diluent can be conducive to the mixing of heat transfer and initiator and monomer.Although any suitable inert diluents can be used Agent, but it is generally selected saturated hydrocarbons, aromatic hydrocarbon, ether, ester, ketone, or combinations thereof.Exemplary diluent includes, but is not limited to Radical of saturated aliphatic and clicyclic hydrocarbon, such as hexane, octane, hexamethylene, petroleum ether etc.；Aromatic hydrocarbon, such as toluene；Aliphatic series and cyclic ether, as Dimethyl ether, diethyl ether, oxolane etc.；Ester, such as ethyl acetate and butyl acetate；And ketone, such as acetone, butanone, etc..

When block copolymer uses active anionic polymerization technology to prepare, simplify structure A-M and can represent activity A block, Wherein M is the initiator fragments selected from the 1st race's metal (such as Li, Na or K).A block is to comprise the methacrylate according to Formulas I The polymerizate of the first monomer composition of monomer.Comprise the second comonomer compositions (e.g., of monomer for forming B block Two monomer compositions can comprise the monomer according to Formula II) may be added to that A-M, result in active two block structure A-B-M.Can wrap Contain the addition of the another kind of charging of the first monomer composition of the monomer according to Formulas I, and the follow-up of active anion site disappears Remove, may result in formation three block structure A-B-A.Or, active two block A-B-M structures can use difunctionality or multifunctional coupling Agent carries out coupling to form three block structure A-B-A copolymer or (A-B)_nStar block copolymer.

Any initiator for active anionic polymerization reaction known in the art can be used.Typical initiator includes Alkali metal hydrocarbon, as organo monolithium compounds is (such as ethyl-lithium, n-pro-pyl lithium, isopropyl lithium, n-BuLi, s-butyl lithium, tertiary pungent Base lithium, positive decyl lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-phenyl butyl lithium, cyclohexyl lithium etc.).This type of single official Energy initiator may be very useful during preparation activity A block or activity B block.Activity for (methyl) acrylate Anionic polymerisation, regulates anion by adding the complexing ligand selected from the such as material of lithium chloride, crown ether or ethyoxyl lithium Reactivity.

The bifunctional initiator being applicable to active anionic polymerization reaction includes but not limited to 1, Isosorbide-5-Nitrae, 4-tetraphenyl-Isosorbide-5-Nitrae- Two lithium butane, 1, Isosorbide-5-Nitrae, 4-tetraphenyl-Isosorbide-5-Nitrae-two lithium iso-butane, and naphthalene lithium, naphthalene sodium, naphthalene potassium and their homologue.Other Suitably bifunctional initiator includes two lithium compounds, as those are by the additive reaction system of lithium alkylide with divinyl compound The compound obtained.Such as, lithium alkylide can be with 1, double (1-phenyl vinyl) benzene of 3-or a di isopropenylbenzene reaction.

When using living radical polymerization technique to prepare block copolymer, the group of other initiators or initiator can be used Close.About living free radical polymerization and the description of the initiator being applicable to these reactions, refer to PCT Patent Publication No.WO97/18247 (Matyjaszewski et al.) and No.WO98/01478 (Le et al.).

Active anionic polymerization is reacted, it is often advisable that initiator is added dropwise over to monomer, until observing The characteristic color relevant to the anion of initiator continues.Then, the initiator of amount of calculation can be added to produce desired molecule The polymer of amount.Preliminary being added dropwise over can destroy the pollutant with initiator for reaction so that can better control over polymerization anti- Should.

Polymerization temperature used depends on be polymerized monomer and the type of polymerization technique used.In general, reaction Can carry out at a temperature of about-100 DEG C to about 100 DEG C.Reacting for active anionic polymerization, temperature typically about-80 DEG C is extremely About 20 DEG C.For living free radical polymerization, temperature is typically about 20 DEG C to about 150 DEG C.Compared to active anionic polymerization Reaction, living free radical polymerization is often less sensitive to variations in temperature.

Generally, polyreaction is carried out under controlled conditions, may destroy initiator or the thing of active anion to get rid of Matter.Generally, polyreaction is carried out in inert atmosphere (such as nitrogen, argon, helium or combinations thereof).When reaction is cloudy for activity During ionic polymerization, anhydrous condition is probably necessity.

Generally, (methyl) acrylate block copolymer can process through melted by heating.This means that they can be through being heated Without there is significant depolymerization in melt process (such as being processed) by extruder or similar devices.(methyl) third Olefin(e) acid ester block copolymer can occur melt-flow at a temperature of greater than about 150 DEG C.The melt-flow temperature of block copolymer Can be regulated by the compatibility (that is, the miscibility) degree between A block and the B block of regulation block copolymer.Such as, may be used To select the composition of A block so that it is comprise offer intensity and the first monomeric unit of required glass transition temperature and change The second comonomer unit of the melt-flow temperature of block copolymer.Suitably second comonomer unit includes (such as) methacrylic acid Cycloalkyl ester, such as cyclohexyl methacrylate etc..The relative quantity of any the first and second available monomers can be used.

Melt-flow regulates also by the weight changing A block and B block.Such as, melt-flow temperature can be passed through Increase the weight of block and be improved, and can be reduced by reducing the weight of block.

A block interacts the most in a different manner with B block, thus be provided with by temperature The characteristic controlled.At a lower temperature (e.g., less than A block glass transition temperature but higher than the glass transition of B block At a temperature of temperature), different blocks is often separated.A block nanometer territory relatively low modulus continuous B block mutually in Rigidity and intensity are provided.

As hereinbefore defined, (methyl) acrylic acid esterbased copolymer can be optical clear or optical clarity.Optics is clear Clear degree is likely to be dependent on the size in A block nanometer territory.In order to realize optical clarity, it is desirable to nanometer territory is less than visible wavelength (about 400 to about 700nm).The average-size in nanometer territory is generally less than about 150nm or less than about 100 nanometers.Can be such as by changing A The content of block or change the chi in nanometer territory by changing the monomer for forming the A block in block copolymer and forming Very little.Unless the refractive index of two phases is the most identical, the biggest domain sizes often causes light scattering.

The binding agent of the present invention also comprises halogen-free flame-retardant.Various different halogen-free flame-retardant can be used.Organophosphor Compound is especially suitable.The suitably example of organic phosphorus compound includes: phosphate ester, aromatic condensation phosphate ester, poly phosphate And phosphinic acid.The object lesson of phosphate ester includes triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, phosphoric acid-2-second Base hexyl diphenyl ester, TRI N BUTYL PHOSPHATE, trixylyl phosphate, resorcinol (double) diphenyl phosphoester and bisphenol-A double (two Phenyl phosphate ester).The object lesson of poly phosphate includes APP, cyanurotriamide modified APP and band coating APP.As used herein, the APP of band coating refers to by with resin coating or encapsulation, resistance to water is improved APP.The object lesson of phosphinic acid is diisooctyl phosphinic acid.The most halogen-containing specially suitable flame-retardant additive bag Include: resorcinol (double) diphenyl phosphoester, bisphenol-A double (diphenyl phosphoester) and can be with trade name SANTICIZER S- 154 triaryls buied from St. Louis Monsanto Company (Monsanto Company, St.Louis, MO) Phosphate ester.

Generally, the most halogen-containing flame-retardant additive adds with the amount that be enough to improve the anti-flammability of binding agent.Implement at some In example, the most halogen-containing flame-retardant additive is with based on (methyl) acrylate group block copolymer and tackifying resin (if present) Gross weight meter at least 10 weight % amount add.In certain embodiments, with based on (methyl) acrylate-based block copolymerization Gross weight meter at least 15 weight % of thing and tackifying resin (if present), 20 weight %, 25 weight %, 30 weight %, 33 weights The amount of amount %, 35 weight % or even 40 weight %, 50 weight % or 60 weight % is added.Due to the most halogen-containing resistance of many Combustion additive generally binding agent is had plasticization effect, it is thus possible to desirably limit its addition to prevent binding agent in Poly-intensity declines.In general, the amount of the most halogen-containing flame-retardant additive of interpolation is based on (methyl) acrylate-based block altogether The gross weight meter of polymers and tackifying resin (if present) is less than 70 weight %.

The binding agent of the present invention also can comprise at least one tackifying resin.Various different tackifying resins are all suitable for.Properly Tackifying resin include (such as) terpene phenolic resin, Colophonium, rosin ester, the ester of hydrogenated rosin, synthesis hydrocarbon resin and they Combination.The suitably example of tackifying resin includes but not limited to be purchased from tennessee,USA Jin Sibo with trade name FORAL Special Eastman Chemical Company (Eastman Chemicals (Kingsport, TN)) or Wilmington,State of Delaware, US Hull gram Those tackifying resins of Li Shi company limited (Hercules Inc. (Wilmington, DE)).Such as, FORAL85, FORAL85E and FORAL85LB (LB refers to low bromine) is the glyceride of rosin acid.FORAL105 and FORAL105E is rosin acid Pentaerythritol ester.FORAL AX and FORAL AX-E is rosin acid.Other suitable tackifying resins include (such as) rosin acid Various glyceride, they can be purchased from U.S.'s famine river chemical industry of Chicago, Illinois, USA with trade name SUPER ESTER Company (Arakawa Chemical, USA (Chicago, IL)), with trade name SYLVALITE or SYLVATAC purchased from U.S.'s Buddhist The Arizona chemical company (Arizona Chemical (Panama CitV, FL)) in Panama City, Flo-Rida-Low state and with business Name of an article PERMALYN is purchased from Eastman Chemical Company (the Eastman Chemicals of tennessee,USA this baud of gold (Kingsport, TN)).Example includes but not limited to: SUPER ESTER W-IOO, SUPER ESTER A-75, SUPER ESTER W-IOO、SUPER ESTER KE-100、SUPER ESTER KE-300、SYLVALITE RE88、SYLVALITE RE100, SYLVATAC RE4265, SYLVATAC RE429 and PERMALYN5095-C.Tackifying resin SUPER ESTER KE- 100 and SUPER ESTER KE-300 are considered as optical clarity.Specially suitable tackifying resin includes SUPER ESTER KE-100, SUPER ESTER A-75 and FORAL85E.

The amount of tackifying resin (if present) changes according to multiple variablees, and these variablees include containing tackifying resin The amount of other components and composition in the desired use of binding agent and binding agent.Generally, tackifying resin is with based on 100 weights existed The amount of amount part (methyl) acrylate group block copolymer meter 1-100 weight portion exists.More commonly, tackifying resin with based on 100 weight portions (methyl) acrylate group block copolymer meter 10-80 weight portion, 20-60 weight portion or the 25-50 weight existed The amount of part exists.

Other additives can be added, as long as these additives are not to contact adhesive group in contact adhesive composition The desired properties of compound adversely affects.In some cases, additive is chosen as A or B with block copolymer Block compatible.If additive causes the glass transition temperature of certain phase (e.g., A block or B block) to offset (assuming that additive With this phase, not there is identical Tg), then this additive is just mutually compatible with this.The example of such additive includes increasing Stick and plasticizer.The reagent of viscosifier or thickening hereinbefore has more detail discussion.It addition, as described above, halogen-free Fire retardant generally may also function as the effect of plasticizer, it is thus possible to need not or need not add extra plasticizer.

Extra additive include antioxidant, filler (such as inorganic filler), ultra-violet stabilizer, softening agent or these add Add the combination of agent.

The suitably example of antioxidant includes those materials based on hindered phenol or sulfur-bearing organic metal salt.These are obstructed Phenol relates to the substituted phenols in ortho position or 2, the dibasic phenols of 5-, and wherein one or more substituent groups are former for having 2 to 30 carbon The band branched hydrocarbyl of son, such as the tert-butyl group or tertiary pentyl.Other available hindered phenols include the phenols of para-orientation, wherein substituent group For alkoxy base, and the alkyl group in alkoxyl is the groups such as methyl, ethyl, the substituted propionic ester of 3-.These sulfur-bearings have Machine slaine relates to the nickel derivant of dibutyl dithiocaarbamate salt.The representative example of commercial antioxidant includes with business The name of an article " IRGANOX1076 " is purchased from American Cyanamid Company purchased from Ciba (Ciba) and with trade name " CYANOX LTDP " The Hinered phenols of (American Cyanamid Co.).

Binding agent also can comprise one or more fillers.Filler does not the most change Tg, but may change storage modulus.Properly The example of filler include organic filler and inorganic filler.The example of organic filler includes (such as) wood flour or starch.More Generally use inorganic filler.The suitably example of inorganic filler includes calcium carbonate, clay, Talcum, silicon dioxide and limited amount White carbon black.The filler of various content can be used to significantly reduce the cost of the adhesive formulation of the present invention.Relatively low content may be right The character impact of binding agent is the least, and higher content may significantly improve rigidity, hardness and deformation resistance.Can use superfine The filler of granularity, such as bentonite or pyrogenic silica are (with trade name " CAB-O-SIL " purchased from Cabot Co., Ltd (Cabot Corporation)), improve the viscosity of solution or give solution thixotropic nature.It addition, if it is desire to binding agent is optical lens Bright or optical clarity, then should select the type of filler, the content of filler and the granularity of filler, in order to avoid the optics to binding agent Character adversely affects.

The suitably example of ultra-violet stabilizer includes UV absorbent (UVA) and hindered amine as light stabilizer (HALS). It is especially useful that the benzotriazole UV A being available from New York, United States Ta Lidun Ciba (Ciba, Tarrytown, NY), all Such as compound TINUVIN P, 213,234,326,327,328 and 571；It is available from New York, United States Ta Lidun Ciba The phenoxy group triazine of (Ciba, Tarrytown, NY), such as TINUVIN400 and 405；It is available from New York, United States Ta Lidun vapour The HALS of Bagong department (Ciba, Tarrytown, NY), such as TINUVIN123,144,622,765,770；And it is available from the U.S. Antioxidant IRGANOX1010,1135 and 1076 of New York Ta Lidun Ciba (Ciba, Tarrytown, NY).Can obtain From the material TINUVIN B75 of New York, United States Ta Lidun Ciba (Ciba, Tarrytown, NY) (containing UVA, HALS and The product of antioxidant) also it is suitable.

Softening agent can be used for (such as) adjust viscosity, improve machinability (such as make adhesive composition be suitable to extrusion), Reduce glass transition temperature thus cause the low temperature adhesion power increased or adjust putting down between cohesive strength and bonding strength Weighing apparatus.Be typically selected to have low volatility, in the visibility region of electromagnetic spectrum for transparent and free or substantially free of color And/or the softening agent of abnormal smells from the patient.If comprising optional softening agent in adhesive composition, then its amount is usually more than 20 weights Amount %, no more than 15 weight %, no more than 10 weight % or no more than 5 weight %.Many adhesive compositions are mediated Suitable softening agent includes but not limited to petroleum base hydro carbons, such as aromatics type (such as naphthalene type) or paraffin wax type；Liquid rubber or derivatives thereof, Such as liquid polybutene resin or hydrogenation of liquid polyisoprene.Suitably polybutene resin can with trade name INDOPOL commercially available from Ineos oligomer company INEOS Oligomers (League City, TX) of Texas, USA Li Gecheng) and with business Name of an article PANALANE (such as, PANALANE H300E) is commercially available from the dish treasured health chemical company of New Jersey Paterson (LIPO Chemicals, Inc. (Paterson, NJ)).In the embodiment adding softening agent, adhesive composition can wrap Containing a kind of softening agent or the combination of softening agent.

(such as stripping is strong except having the character the most relevant with binding agent (such as contact adhesive) for the binding agent of the present invention Degree, shearing retentivity and cohesiveness) beyond, also there is other ideal characterisitics.These characteristics relate to anti-flammability, and at some Embodiment relates to preferable optical property (such as presenting optical clear or optical clarity).

Develop multiple different testing scheme to measure the anti-flammability of material (such as binding agent).Selection to scheme Depend on many factors, the desired use of such as binding agent.Generally, with the form of adhesive article, binding agent is tested, That is binding agent is coated on backing or base material to test.

Suitably testing scheme relates to vertical combustion testing FAR25.853a.This test EXAMPLEPART below has in detail Thin description.Multiple embodiments of the flame-retardant pressure-sensitive binding agent of the present invention are logical when being applied on THV-500 or Polyurethane backings Cross this test.But, even if not being likely to by the embodiment of the flame-retardant pressure-sensitive binding agent of the present invention of this test By different testing schemes, and therefore for some is applied, it is probably suitable flame-retardant pressure-sensitive binding agent.

Some embodiments of fire retardant adhesive are optical clear or optical clarity.As it has been described above, " optical clear " refers to system Product, film or binding agent visible light (about 400nm to about 700nm) at least some of on there is high transmission rate.Similarly, As it has been described above, " optical clarity " refer to visible light (about 400nm to about 700nm) at least some of on there is high transmission rate And present binding agent or the goods of low haze.(such as) ASTM-D1003-95 can be used to measure light transmission and mist degree.Separately Outward, commercially available for the spectrophotometer of test sample, it directly generates light transmission and haze value.The example of this quasi-instrument Attached bag includes (such as) can be from the commercially available TCS Plus light splitting of Bi Ke-Gardner company limited (BYK-Gardener, Inc.) Photometer.

Optical clarity or optical clarity can be controlled by multiple technologies.These technology relate to (such as) to (methyl) third Olefin(e) acid ester group block copolymer carries out selecting, selects halogen-free flame-retardant, to any other adds present in binding agent Add agent (such as viscosifier, plasticizer, antioxidant, filler and ultra-violet stabilizer) to select.Any additive existed Granularity is probably particular importance.

Optical clarity or optical clarity are likely to be dependent on (methyl) acrylate group block copolymer.Particularly important It it is the size in A block nanometer territory.The average-size in this nanometer territory is generally less than about 150 nanometers or is even less than about 100 nanometers.Receive The size in rice territory can (such as) by the content of A block or be controlled by the monomer composition of A block in block copolymer. Unless the refractive index of two phases (A block phase and B block phase) is the most identical, the biggest nanometer domain sizes often causes light Scattering.

The embodiment of the flame-retardant pressure-sensitive binding agent of optical clarity is generally of the % absorbance of at least 90% and is less than The mist degree of 10%.The embodiment of the flame-retardant pressure-sensitive binding agent of optical clarity is generally of the % absorbance of at least 95% and is less than The mist degree of 5%.It addition, some embodiments of the flame-retardant pressure-sensitive binding agent of optical clarity have in the range of about 0.16 to 2.0 Yellowing factor b*.

It will be recognized that some optical characteristics can use L*, a* and b* colour code to be defined.L*, a* and b* value is based on The method of CIE (Intemational Commission on Illumination, international lighting association), the method makes to be used as The test absorbance of material of function or reflectance, the spectral power of selected standard illuminants and CIE mark for lambda1-wavelength The color matching functions of quasi-observer determines its colour code.Determine that the CIE process of L*, a* and b* value is at ASTM E308 and ASTM E1164 has a detailed description.ASTM E308 discusses use CIE system to calculate the standard operation of object color, and ASTM E1164 discusses the standard operation obtaining Spectrophotometric Data for object-color evaluation.Herein cited L*, a* and b* value It is to use absorbance, CIE standard illuminants C (expression daylight) and the color of 2 degree of CIE standard observer in visible light Adaptation function determines.

For given object, L*, a* and b* colour code serves as the seat of particular coloured regions described in the three-dimensional color space Mark.A* value and b* value describe tone and the saturation of color.Such as, positive a* value is positioned in red area, and negative a* value It is positioned in green area.Positive b* value is positioned in yellow area, and negative b* value is positioned in blue region.A* value and the symbol of b* value Number (plus or minus) determines the tone of optical bodies, and its absolute value determines the saturation of this concrete tone.

The absolute value increased is corresponding to higher saturation.L* coordinate relates to intensity or the brightness of optical bodies.Bigger Positive L* value corresponding to white portion, and close to zero less L* on the occasion of corresponding to black region.A* and b* when optical bodies When colour code is close to zero, this corresponds to neutral color or gray area.Therefore, in order to obtain gray appearance, a* and b* colour code exhausted Value should be about 5 or less.It is highly preferred that the absolute value of a* and b* colour code should be about 3 or less.

Although L*, a* and b* colour code can accurately measure after arithmetic point several, but the significant difference between colour code is usual Can be discovered by human eye.The difference of colour code is discovered in the change of human eye color or " colourity (shade) " by noting object. Generally, only when the absolute value of the difference of colour code is about 1 or bigger, human eye just can perceive its difference.Therefore, if it is considered to The colour code of the first material and the corresponding colour code of the second material are different, then the absolute value of the difference of two kinds of corresponding colour codes should be about 1 or Bigger, more preferably about two or more.

The binding agent of the present invention can be prepared by multiple technologies.The preparation method of described binding agent is as follows: by (first Base) halogen-free flame-retardant of acrylate group block copolymer and at least 10 weight % is blended.Blend can be prepared in a solvent Maybe can be prepared as solvent-free blend.As set forth above, it is possible to add extra component in adhesive blends, such as a kind of or Multiple tackifying resin, antioxidant, filler, ultra-violet stabilizer, plasticizer or combinations thereof.

In certain embodiments, adhesive blends is prepared in a solvent.Solvent can include single solvent or different solvents Mixture.Generally, if using different solvents, then these solvents are compatible with each other.Comprise (methyl) acrylate-based block The solvent mixture of the halogen-free flame-retardant of copolymer and at least 10 weight % can use multiple different method to be prepared. Component each can be dissolved and the most then carry out mixing (being mixed by solution), a kind of component can be dissolved in a solvent Then add and dissolve other components (adding component to solution), or can be by admixed together with drying regime for two kinds of components Then it is made to dissolve by adding solvent.As it has been described above, solvent can refer to single solvent, or it can be the mixing of solvent Thing.

In order to dissolve (methyl) acrylate group block copolymer, the solvent of selection needs embedding for the A of block copolymer It is all good solvent for section and B block.The suitably example of solvent includes: ketone, such as acetone and methyl ethyl ketone；Ether Class, such as ether and oxolane；Esters, such as ethyl acetate；Alkanes, such as hexane, heptane and petroleum ether；Aromatic hydrocarbon, such as benzene and Toluene；And combinations thereof.In certain embodiments, toluene, ethyl acetate, oxolane and methyl ethyl ketone are for especially to manage The solvent thought.

For dissolving halogen-free flame-retardant, any one in solvent listed above is the most applicable.In certain embodiments, first Benzene, ethyl acetate, oxolane and methyl ethyl ketone are particularly desirable solvent.Similarly, add in adhesive blends Any extra additive (such as tackifying resin) as solution (having dissolved in a solvent) or can add in a dry form.

No matter for the order of addition forming binder solution blend, binder solution blend usually contains about The solid of 30 weight % to about 70 weight %, say, that the dry weight of solid constituent (polymer, fire retardant, additive etc.) accounts for molten The 30-70% of liquid gross weight.

Adhesive article to be formed, is coated to solvent type adhesive blend on base material.This base material can be (such as) Adhesive tape backing, the surface of goods or barrier liner.The suitably example of adhesive tape backing includes (such as) paper and polymeric film.Paper The example opened includes being coated with the paper of clay and being coated with the paper of polyethylene.The example of polymeric film include containing a kind of or The film of multiple polymers, described polymer such as cellulose acetate-butyrate；Cellulose-acetate propionate；Cellulose triacetate；Poly-(first Base) acrylate, such as polymethyl methacrylate；Polyester, such as polyethylene terephthalate and poly-naphthalenedicarboxylic acid Glycol ester；Copolymer based on naphthalene dicarboxylic acids or blend；Polyether sulfone；Polyurethane；Merlon；Polrvinyl chloride；Between rule vertical Structure polystyrene；Cyclic olefine copolymer；Polyolefin, including polyethylene and polypropylene, such as curtain coating and the polypropylene of biaxial orientation； And fluorine-containing thermoplastic polymer.Base material can include single or multiple lift, such as, be coated with the poly terephthalic acid second of polyethylene Diol ester.This base material can scribble priming paint or treated to give some required characteristics to one or more surface.At these The example of reason includes sided corona treatment, flame treatment, plasma treatment and chemical treatment.Specially suitable adhesive tape backing is by gathering benzene Naphthalate (PET) is made, is made up of polyurethane or is made up of fluorine-containing thermoplastic polymer.Specially suitable backing material Material is for can be from the commercially available fluorine-containing thermoplastic of the Tai Liang company (DYNEON, Oakdale, MN) of Minn. omeprazole Dai Er Property material THV500, and can be from Lubrizol Corp. (Lubrizol, Cleveland, OH) of Ohio, USA Cleveland Commercially available polyether thermoplastic polyurethane ESTANE58244 and ESTANE58277.

In other embodiments, base material is the surface of goods.Various products surface is all suitable for, and it can be rigid surface (such as metallic plate, glass plate etc.) or flexible surface (such as fabric, weaving and nonwoven web, foam, flannelette blanket, metal forming etc.).

Base material can also is that barrier liner.Any suitable barrier liner can be used.Exemplary barrier liner include by Paper (such as kraft paper) or polymeric material (such as, polyolefin such as polyethylene or polypropylene, ethene-vinyl acetate, poly-ammonia Ester, polyester such as polyethylene terephthalate, etc.) prepare those.At least some of barrier liner is coated with release agent layer, The such as material containing organosilicon or the material containing fluorocarbon.Exemplary barrier liner includes, but is not limited to can be with commodity Name " T-30 " and " T-10 " is purchased from Martinsville, Virginia, The United States state head Nuo Kete functional membrane company (CP Film (Martinsville, Va.)) liner, described liner have on polyethylene terephthalate film organosilicon isolation be coated with Layer.Described liner can have micro structure in its surface, and it is micro-that this makes described binding agent can be formed in adhesive layer surface Structure.The most removable liner, makes the adhesive phase with microstructured surface expose.

Because in certain embodiments, binding agent is optical clear or optical clarity, and therefore resulting product can be light Learn element or may be used for preparing optical element.As used herein, term " optical element " refers to have optical effect or optics The goods of application.Optical element can be used for such as electronic displays, Application in Building, transmission application, projection application, photonics applications Apply with figure.Suitably optical element includes but not limited to screen or display, cathode ray tube, polariser, reflector etc..

Any suitable blooming can be used in goods.As used herein, term " blooming " refers to can be used for producing light Learn the film of effect.Blooming usually contains the film of polymer, and it can be single or multiple lift.Blooming is flexible, and Can have any suitable thickness.The blooming some wavelength (visual field, ultra-violet (UV) band or red such as electromagnetic spectrum to electromagnetic spectrum The wavelength of outskirt) generally at least fractional transmission, reflection, antireflecting, polarization, optical clarity or diffusion.Show The blooming of example include but not limited to visible light microscopic film, coloring mirror film, sunlight reflectance coating, infrared reflection film, ultraviolet reflectance film, Reflective polarizer films (such as brightness enhancement film and dual brightness enhancement thin film), absorb polarizing coating, optical clarity film, Coloured film and anti- Reflectance coating.

In certain embodiments, blooming has coating.Generally, coating is used for the function of reinforcing membrane, or provides for film Other function.The example of coating includes (such as) hard conating, antifogging coating, anti-scraping coating, peep-proof coating or combinations thereof. In such as touch panel sensor, display screen, figure application etc. are applied, such as hard conating, antifogging coating and offer strengthen durable The coatings such as the anti-scraping coating of property are desirable.The example of peep-proof coating includes the coating that (such as) is fuzzy or vaporific, to obtain Cover sight line or the film of louvered thus limit visual angle.

Some blooming has multilamellar, such as the multilamellar of the material (polymer as with or without dyestuff) containing polymer, Or contain material and the multilamellar of polymeric material of metal.Some blooming has replacing of the different polymeric material of refractive index Layer.Other bloomings have polymeric layer alternately and metal-containing layer.Exemplary blooming is described in following patent: United States Patent (USP) No.6,049,419 (Wheatley et al.), United States Patent (USP) No.5,223,465 (Wheatley et al.), the U.S. are special Profit No.5,882,774 (Jonza et al.), United States Patent (USP) No.6,049,419 (Wheatley et al.), United States Patent (USP) No.RE34, 605 (Schrenk et al.), United States Patent (USP) No.5,579,162 (Bjornard et al.) and United States Patent (USP)s No.5,360,659 (Arends et al.).

Solvent type adhesive blend can be coated with by any suitable technique, such as by (as) blade coating, roller coat, recessed Version printing coating, rod painting, curtain and airblade coating.Also can be by known method printing binder blend, example Such as silk screen printing or ink jet printing.Then, usual dry adhesive coating is to remove solvent.In certain embodiments, coating warp By the high temperature such as supplied by baking oven (such as, convection oven), in order to accelerate binding agent and be dried.

Adhesive blends can also use solvent-free process (such as melt compounding) to be prepared.Multiple melt compounding skill Art is suitable to prepare the contact adhesive of the present invention, and these technology use multiple hot melt mixing device.Both interval mixing can have been used Equipment can use again continuous-blending equipment.The example of discontinuous method includes that those use Bradley originally to reach instrument (BRABENDER) (as can be from New Jersey Nan Hakensake C.W. Brabender Instrument Ltd. (C.W.Brabender Instruments, Inc., South Hackensack, NJ) commercially available Bradley originally reaches preparation center (BRABENDER PREP CENTER)) or Banbury (BANBURY) internal-mixing and rolling formula equipment (be such as available from Connecticut, USA peace Sony The equipment of sub-Farrel Corp. (US) 25 Main Street, Ansonia, CT 06401, U.S.A. (Farrel Co., Ansonia, CN)) method.The example of continuation method includes that single screw rod squeezes Go out, twin-screw extrusion, disk extrusion, reciprocating Single screw extrusion and pin barrel Single screw extrusion.Continuation method can use point Join element, pin hybrid element, static mixing element and dispersive element such as MADDOCK hybrid element and SAXTON hybrid element. Single melt compounding device can be used or the combination of hot melt mixing device can be used to be blended to the hot melt preparing the present invention Thing and contact adhesive.In some embodiments, it may be desirable to use a more than hot melt mixing device.Such as, one Extruder (such as single screw extrusion machine) can be used for (methyl) acrylate group block copolymer is carried out heat fusing process.This squeezes The output going out machine can be fed in the second extruder (such as double screw extruder) with the component melt compounding with other.

It is applied on base material form adhesive phase by the output of melt compounding.If use batch equipment, can be from dress Put taking-up hot melt blend, be placed in hot melt coater or extruder and be applied on base material.If using extruder to prepare Hot melt blend, can directly be expressed into blend on base material and form adhesive phase with continuous print forming method.Described above Be suitable to the example of the base material being used together with solvent-borne type coating process.In being formed continuously method, binding agent can be pulled out Film die head also contacts plastics web or other suitable base materials of movement subsequently.If it is desired that binding agent is a part for adhesive tape, Then base material can be adhesive tape backing.In certain methods, then adhesive tape backing material and binding agent from film die head coextrusion and will Described multi-ply construction cools down and forms adhesive tape in individually coated step.If it is desired that binding agent is transfering belt, then binding agent Layer can be self-supported membrane, and base material can be barrier liner or other release base materials.After formation, can be by using direct method (such as chill roll or water-bath) and indirect method (such as air or gas spray) quenching makes adhesive phase or film hardening.

It is also possible to use solvent-free mixing and the combination of coating technique with solvent-borne type.Such as, solvent type adhesive can be prepared Blend, is subsequently dried and heat seeling coating.Similarly, Hot melt adhesive blends can be dissolved in one or more solvents also It is coated.

The thickness using the coated adhesive phase of solvent-borne type coating process or solvent-free coatable method will depend upon which multiple Factor, including the desired use of adhesive article.Generally, the thickness of adhesive phase is commonly greater than about 5 microns (μm), greater than about 10 μm, greater than about 15 μm or even greater than about 20 μm.This thickness is frequently less than about 1000 μm, less than about 250 μm, less than about 200 μm Or it is even less than about 175 μm.Such as, this thickness can be about 5 to about 1000 μm, about 10 to about 500 μm, about 25 to about 250 μm Or about 50 to about 175 μm.

The disclosure includes the following example.

These embodiments relate to binding agent.First embodiment includes that binding agent, described binding agent comprise: (methyl) acrylic acid Ester group block copolymer；The halogen-free flame-retardant of at least 10 weight %, wherein said binding agent is flame-retardant pressure-sensitive binding agent.

Embodiment 2 is the binding agent of embodiment 1, and wherein said contact adhesive is optical clarity.

Embodiment 3 is the binding agent of embodiment 1 or 2, and described binding agent also comprises the additive that at least one is extra.

Embodiment 4 is the binding agent of embodiment 3, at least one additive wherein said include tackifying resin, antioxidant, Inorganic filler, ultra-violet stabilizer, UV absorbent, plasticizer, softening agent or combinations thereof.

The embodiment 5 binding agent any one of embodiment 1-4, wherein (methyl) acrylate group block copolymer includes (methyl) acrylate diblock, three blocks or star block copolymer.

The embodiment 6 binding agent any one of embodiment 1-5, wherein (methyl) acrylate group block copolymer includes Triblock copolymer, this triblock copolymer comprises: at least two A end-blocks polymer unit, and described A end-blocks is polymerized Thing unit each derived from including the first monoethylenically unsaturated monomer of (methyl) acrylate, styrene or combinations thereof, The most each A end-blocks has the glass transition temperature of at least 50 DEG C；With at least one B mid block polymers unit, Described B mid block polymers unit is derived from the second monoene key unsaturation list including (methyl) acrylate or vinyl esters Body, the most each B mid-block has the glass transition temperature of no more than 20 DEG C；And wherein the first monoene key unsaturation list At least one in body or the second monoethylenically unsaturated monomer includes (methyl) acrylate monomer.

Embodiment 7 is the binding agent of embodiment 6, and wherein (methyl) acrylate based triblock copolymer includes (poly-methyl Acrylic acid methyl ester .)-(polyalkyl acrylate)-(polymethyl methacrylate) copolymer.

Embodiment 8 is the binding agent of embodiment 7, and wherein said polyalkyl acrylate block constitutes polymer, and this gathers Compound comprises at least one acrylate monomer, and this acrylate monomer has the alkyl containing 1-20 carbon atom.

Embodiment 9 is the binding agent of embodiment 2, and the % absorbance of the flame-retardant pressure-sensitive binding agent of wherein said optical clarity is At least 90%, and mist degree is less than 10%.

Embodiment 10 is the binding agent of embodiment 2, the % absorbance of the flame-retardant pressure-sensitive binding agent of wherein said optical clarity It is at least 95%, and mist degree is less than 5%.

The embodiment 11 binding agent any one of embodiment 2,9 or 10, the fire retardant pressure sensitive of wherein said optical clarity glues Mixture has the yellowing factor b* in the range of about 0.16 to 2.0.

The embodiment 12 binding agent any one of embodiment 1-11, wherein said flame-retardant pressure-sensitive binding agent is when being coated to the back of the body Passed through during lining vertical combustion test FAR25.853a, described backing comprise polyethylene terephthalate, polyurethane or Fluorothermoplasts.

The embodiment 13 binding agent any one of embodiment 1-12, the most halogen-containing wherein said flame-retardant additive includes Organic phosphorus compound.

Embodiment 14 is the binding agent of embodiment 13, and wherein said organic phosphorus compound includes phosphate ester, aromatic condensation Phosphate ester, poly phosphate, phosphinic acid or combinations thereof.

Embodiment 15 is the binding agent of embodiment 14, and wherein said organic phosphorus compound includes resorcinol (double) diphenyl Phosphate ester, bisphenol-A double (diphenyl phosphoester) or triaryl phosphate.

The method that these embodiments relate to preparing binding agent.Embodiment 16 includes the method preparing binding agent, described method Including: (methyl) acrylate group block copolymer is provided；Halogen-free flame-retardant is provided；And by acrylate-based to (methyl) embedding Section copolymer is blended with halogen-free flame-retardant, and to form contact adhesive, wherein said halogen-free flame-retardant accounts for binding agent extremely Few 10 weight %.

Embodiment 17 is the method for embodiment 16, and wherein said contact adhesive is optical clarity.

Embodiment 18 is the method for embodiment 16 or 17, and the method also includes providing in binding agent and at least one being blended Extra additive.

Embodiment 19 is the method for embodiment 18, and at least one extra additive wherein said includes tackifying resin, resists Oxidant, inorganic filler, ultra-violet stabilizer, UV absorbent, plasticizer, softening agent or combinations thereof.

The embodiment 20 method any one of embodiment 16-19, is wherein blended and includes hot melt elder brother altogether.

Embodiment 21 is the method for embodiment 20, and wherein hot melt is blended and includes (methyl) acrylate group block copolymer Add to extruder the hot melt blend of extruding gained with halogen-free flame-retardant.

The embodiment 22 method any one of embodiment 16-19, wherein said contact adhesive also comprises at least one Solvent, and be blended include solvent be blended.

Embodiment 23 is the method for embodiment 22, wherein provides (methyl) acrylate group block copolymer to include providing molten Solution in (methyl) acrylate group block copolymer of solvent.

Embodiment 24 is the method for embodiment 20, also includes being coated on base material contact adhesive hot melt.

Embodiment 25 is the method for embodiment 22, also includes contact adhesive solvent coating on base material.

Example

These examples are only used for exemplary purpose, and have no intention to limit scope of the following claims.Unless it is another Indicate outward, otherwise all the pressing with all numbers in lower part and claims, percent, ratio etc. of example and description Weight meter.Following instance use these abridge: g=gram, mg=milligram, min=minute, h=hour, the sec=second, mL=milliliter, L= Rise, the s=second, rpm=rev/min, cm/min=cm per minute, ft/min=feet/min, kJ=Kilojoule, mil=one thousandth English Very little.Except as otherwise noted, otherwise solvent for use and other reagent are purchased from the Sigma in Milwaukee, WI, USA city Aldrich Chemical company (Sigma-Aldrich Chemical Company, Milwaukee, Wisconsin).

Abbreviation table

Method of testing

Vertical combustion is tested

Standard that this method of testing is based on and program follow F.A.R. the 25.853rd article (July nineteen ninety) regulation but Being different from the regulation in F.A.R. the 25.853rd article (July nineteen ninety), difference is that sample (sample) is in 50% ± 10% phase The shortest 24 hours to adapting under humidity, rather than adapt under 50% ± 5% relative humidity of regulation.

Sample adapts to the shortest 24 hours under 21.1 DEG C ± 2.8 DEG C (70 °F ± 5 °F) and 50% ± 10% relative humidity.Will Sample is loaded in U-shaped metal framework so that two long limits and narrow edge is vertical orientated securely fixes, not by substrate support And be not attached on base material.The exposed area of sample is that at least 50.8mm (2 inches) width × about 304.8mm (12 inches) is long.

Sample is made to be exposed to the flame of Bunsen burner burner (Bunsen bumer).The lower limb of sample is upper than burner Edge exceeds about 19.1mm (3/4 inch).Flame is put on the centrage 12 seconds or 60 seconds of sample lower limb (according in example Regulation).Record burning time, burning length, particle burning to the time extinguished and burning particles molten drop number are (if had Words).Burning length is to be damaged due to flame injection from the initial edge of the sample being exposed to flame to test sample Distance between solstics, including partially or completely burnouting, carbonization or the region of embrittlement, but do not include by sooting, stain, warpage Or the region faded or material are away from shrinking at thermal source or melted region.

F.A.R. when the 25.853rd article (July nineteen ninety) item (a) (1) (i) carries out 60 seconds fire exposure, it is desirable to average combustion Length is less than 152.4mm (6 inches), removes the average burning time after flame source less than 15 seconds, and after molten drop drippage The average time burnt away is less than 3 seconds.F.A.R. the 25.853rd article of (July nineteen ninety) item (a) (1) (ii) carries out 12 seconds fire When flame exposes, it is desirable to average combustion length is less than 203mm (8 inches), remove the average burning time after flame source and be less than The average time burnt away behind 15 seconds, and molten drop drippage was less than 5 seconds.

Peel adhesion strength test

This test is measured and is peeled off required power from base material with 180 degree of angles.This test uses the ASTM test side of reference Program described in method ASTM D3330/D3330M-04, use base material hereinafter described for example prepares through adapting to Adhesive tape is carried out.

The peel adhesion peeled off from glass:

By adhesive tape wide to 12.7 millimeters (12.7mm) is adhered to glass plate, and roll once on adhesive tape with 2kg roller And prepare test sample.With the plate speed of 12 inch/minute (305 mm/min (mm/min)) to glue on tension tester Band is tested.Each example is tested two samples.Meansigma methods records with ounce/inch (oz/in), and be converted to newton/ Decimetre (N/dm).

The peel adhesion peeled off from aluminium sheet, glass mat and carbon fiber board:

By 25.4mm (1 inch) wide adhesive tape is adhered to base material (aluminium sheet, glass mat and carbon fiber board), and use 2kg roller rolls on adhesive tape 20 times and prepares test sample.Under 23 DEG C/50%RH after pressurize 24 hours, at tension tester On with the plate speed of 12 inch/minute (305 mm/min (mm/min)), adhesive tape is tested.To each test sample three Individual sample.Meansigma methods records with ounce/inch (oz/in), and is converted to newton/decimetre (N/dm).

Shear strength is tested

The Static Shear Strength in minutes of adhesive tape is measured in this test.This test uses the ASTM Test Method of reference Program described in ASTM D-3654/D3654M06, use variations hereinafter described for example prepares through adapting to Adhesive tape carry out.Tape terminal is adhered to the corrosion resistant plate becoming an angle of 90 degrees to hang with vertical line, and counterweight is attached to adhesive tape Free end.Test is carried out under room temperature (RT) or under high temperature (70 DEG C).

70 DEG C of shearing tests: prepared test sample by the adhesive tape through adapting to prepared in instances.By 12.7mm (0.5 English Very little) wide adhesive tape adheres to one side of corrosion resistant plate so that its 25.4mm overlapping with panel (1 inch), then use the roller of 2kg The part of adhesive tape being attached to panel rolls twice.0.5kg load is attached to the free end of adhesive tape, is being set as 70 DEG C Baking oven in become an angle of 90 degrees to hang panel with vertical line.Measure the time in minutes that adhesive tape is pulled away from from panel, and record inefficacy Time and failure mode.Possible failure mode is wherein to pull off " the adhesion of binding agent neatly from panel or adhesive tape backing (a) ", or " the cohesiveness that wherein binding agent divides, some adhesive is stayed on adhesive tape and is partially left on adhesive tape backing (c)”.If 10, lost efficacy in 000 minute, then end of test, result was recorded as " 10,000 minutes ".By data It is reported as the arithmetical average of three measured values.

RT shearing test: prepare and test test sample with the method identical with 70 DEG C of shearing tests, except for the difference that by 1kg Counterweight is attached to adhesive tape, and test panel is suspended in controlled environment room (23 DEG C/50% relative humidity).

Micro combustions calorimetry method of testing

This test is carried out according to ASTM D7309-07 method A code.The instrument used is MCC-2 type Govmark MCC. Conventional method is included in nitrogen environment the speed with 1 DEG C/sec and heats 1-5mg sample.Catabolite is in a combustion chamber Complete oxidation, the temperature of combustor remains 900 DEG C, and environment is 20% oxygen and 80% nitrogen.The heat release of decomposition gas Determined by the oxygen quality being used for decomposing completely sample.To each sample test three times to be estimated, result is averaged. Following parameters is calculated: heat discharges capacity η by data_c(J/g-° of K)-it equal to high specific HRR divided by the rate of heat addition；? Big specific heat release Q_max(W/g) maximum in-whole temperature range；The temperature of hot release temperature (K)-maximum specific heat release；With And specific heat release h_c(kJ/g) the clean heat release in-whole temperature range.

Light transmission and haze measurement

This test is carried out according to ASTM method 1003.(Bi Ke-Gardner has to use 8870 type TCS Plus spectrophotometers Limit company (BYK-Gardner, Inc.)) light transmission and the mist degree of adhesive coating are measured.Use CIE standard illuminants Body A.Adhesive coating on barrier liner is transferred to glass microscope-slide (a size of 75mm × 50mm), and mode will be for gluing Mixture is pressed into blend rubber roller on slide glass and applies pressure.For absorbance and color measuring, subsequently barrier liner is removed, from And on glass microscope-slide, obtain adhesive composition.Use the measurement result not containing sample in spectrophotometer as ginseng Examine (reference: absorbance=100%, b*=0 and mist degree=0%), record % light transmittance, b* parameter and % mist degree.

Tensile test method

The band of 2.54 cm x 1.27 centimetres (1 inch × 0.5 inch) is placed on cupping machine (4501 types Instron, derives from Massachusetts, United States Canton Instron Corporation (Instron Co., Canton, MA)) two fixtures Between.Described fixture is with 12, and " speed of/min (305 mm/min (mm/min)) separates, and record makes the power needed for ribbon breaks (record with psi, and be converted to kPa) and breaking strain percentage ratio (%).

Synthesis example

SE-1: generate acrylic acid series triblock copolymer IBOMA-20A-IBOMA

Use following active free radical polymerization method prepare acrylic acid series triblock copolymer isobornyl methacrylate- Co-acrylic acid 2-monooctyl ester-co-isobornyl methacrylate.

Step 1: prepare the poly-2-OA mid-block macromole evocating agent that molecular weight is 85,000:

The 2-OA of 300g is passed twice through and is filled with inhibitor and removes resin (AlfaAesar company (Alfa Aesar)) Pillar also collects product.2-OA purified for 283g is added in the round-bottomed flask equipped with 180g toluene, close with rubber septum Envelope flask with nitrogen bubble 30 minutes.By 0.115g copper bromide (II) and 0.15g M₆Tren (the limited public affairs of ATRP solution Department (ATRP Solutions INC.)) it is dissolved in the dimethylformamide of 9g, seal and with nitrogen bubble five minutes.Then By syringe, this solution of 4mL is transferred in the round-bottomed flask of sealing.By 1.1g1,4--dibromo adipic acid and 0.38g ethyl Caproic acid stannum (II) (aldrich company (Aldrich)) is dissolved in 4g toluene, seals and with nitrogen bubble 5 minutes.Then lead to Cross syringe to be transferred in bigger round-bottomed flask by this solution of 3mL.Then use oil bath that round-bottomed flask is heated to 70 DEG C, and Keep 48 hours at such a temperature.Using nuclear magnetic resonance, NMR (NMR) to measure monomer conversion, result is of about 90%.Gel infiltration It is 84,800 grams/mol that chromatography (GPC) is analyzed to identify molecular weight.Rotary Evaporators is used to remove solvent and residual monomer, To macromole evocating agent product.

Step 2: mid-block p20A is blocked with IBOMA

The 150g macromole evocating agent that step 1 is obtained and 0.6g copper bromide (II) solution prepared in above-mentioned steps 1 It is dissolved in 60g toluene.This solution is prepared in bigger sealed flask, then uses nitrogen bubble 20 minutes.By 200g IBOMA passes twice through and is filled with inhibitor and removes the pillar of resin (AlfaAesar company (Alfa Aesar)) and collect product. IBOMA with 1.7g thylhexoic acid stannum (II) purified for 120g is mixed in sealing container, uses nitrogen bubble 20 minutes subsequently. It is transferred to, equipped with in the sealing container of macromole evocating agent, be heated also at 65 DEG C by this flask by this solution of 20g by syringe Keep 24 hours.GPC display polymer molecular weight is 106,000 grams/mol.¹H-NMR analyzes and shows, in triblock copolymer The ratio of 2-OA Yu IBOMA substantially 85:15.Triblock copolymer is deposited in cold methanol and separates, collect, and very Empty baking oven is dried overnight.

Micro combustions calorimetry test screen

Use above-mentioned micro combustions calorimeter method of testing that various polymeric material samples are screened.Result is at Table A Shown in.Sample A and C-F uses as it is.Prepare by 0.65gABC-2 and 0.35g FR-1 being dissolved in 1 gram of toluene Sample B.2-5mg sample (sample A and C-F) is cut from solid material.For sample B, the 2-5mg drop-coated of solution is layed onto On barrier liner, to the thickness of about 51 microns (2 mils), then at 110 DEG C of dry 30min, obtain 2-5mg solid sample.

Table A

Preparation is coated with the adhesive tape of acrylic block copolymer adhesive:

Example 1-24 and comparative example C1-C15:

By preparing binder solution and preparing a series of adhesive coatings with this solution of solvent coating.Subsequently general Operation is:

Rotate overnight at room temperature on roller mill by being placed in tank, and by acrylic block copolymer (ABC-1, ABC-2 or ABC-3) pellet with or without viscosifier (Tack-1, Tack-2 or Tack-3) together and with or without Halogen Element fire retardant (FR-1) is dissolved in toluene together, obtains the solution that concentration is 50 weight % solids.Composition shows in table 1 below Go out.With knife coater, all solution are coated on backing, obtain the dry coating layer thickness of about 51 microns (2 mils). Then painting is placed in convection oven, at 70 DEG C, is dried 15min, is then saved in steady temperature (23 DEG C) and constant The indoor of humidity (RH50%).

Table 1

Example 25-27 and comparative example C18-C21:

A series of adhesive coating is prepared by hot melt cladding process.General procedure subsequently is:

Amount is sent into taper for the acrylic block copolymer of 150g, viscosifier, halogen-free flame-retardant and antioxidant Double screw extruder.Composition is shown in table 2 below.Making compositions is 177 DEG C to 204 DEG C (350 °F to 400 °F) in temperature range Compounding district in (from 1st district to 10th district) carry out mixing and melting, and this process is at motor 1127rpm and the pressure of screw rod 300rpm Under carry out.After heating at the same time and being compounded 3 minutes under conditions of mechanical agitation, pressure is reduced, make motor and screw rod be respectively 376rpm and 100rpm.Then under the pressure of 100rpm and the linear velocity of 240cm/min (8ft/min), binding agent is pumped into painting Layer gap, it is thus achieved that the thick adhesive phase of 51 microns (2 mil) between two silicon liner.After preparing adhesive tape sample, will Adhesive phase is laminated to thin film back lining.

Table 2

The flame-retarding characteristic of acrylic block copolymer adhesive tape:

Use the binding agent being coated on backing that above-mentioned vertical combustion method of testing test prepares according to the method described above The flame-retarding characteristic of layer sample.Being configured to of being tested be coated in the adhesive phase on backing (band) or wherein slice layer be pressed onto Structure on panel.It is 12 seconds or 60 seconds (as shown in Table) in the combustion testing time that table 3 comprises the sample of employing solvent coating In the case of vertical combustion test data.Table 4 comprises the sample of hot melt coating in the case of the combustion testing time is 12 seconds Vertical combustion test data.

Table 3

Table 4

The adhesive properties of acrylic block copolymer adhesive tape:

Being prepared as being similar to above-mentioned adhesive tape sample by the adhesive tape sample being used for binding agent test, difference is to use Thin film-1 is as backing.As described in above-mentioned method of testing, the shear strength of test sample (RT and 70 DEG C at) and from glass plate, The peel adhesion peeled off on aluminium sheet, glass mat and carbon fiber board.Use the data of sample of solvent coating in table 5 below Present, and use the data of the sample of hot melt coating to present in table 6 below.

Table 5

NT=does not tests

Table 6

Adhesive coating aging:

One of following two set conditions are used to carry out in the sample of adhesive coating prepared as described above aging: at 70 DEG C Aging 168 hours, under 50 DEG C/95% relative humidity aging 168 hours.After overaging, the sample of adhesive coating is put Put in CTH room (23 DEG C/50%RH) 24 hours, then perform RT and 70 DEG C of shearing tests.The sample using solvent coating presents In table 7, the sample using hot melt coating presents in table 8.

Table 7

Table 8

The optical property of acrylic block copolymer adhesive:

According to method of testing given above, the optical property of selected coated adhesive sample is tested.Result It is shown in Table 9.

Table 9

The mechanical performance of acrylic block copolymer adhesive:

According to method of testing given above, the mechanical performance of selected coated adhesive sample is tested.Result It is shown in Table 10.

Table 10

Claims (17)

1. a binding agent, it consists of:

(methyl) acrylate group block copolymer；

The halogen-free flame-retardant of at least 10 weight %, and

A kind of extra additive,

Wherein said binding agent is flame-retardant pressure-sensitive binding agent, and at least one additive described is selected from tackifying resin, antioxidant, nothing Machine filler, ultra-violet stabilizer, plasticizer, softening agent or combinations thereof,

Weight % of wherein said halogen-free flame-retardant is based on described (methyl) acrylate group block copolymer and optional increasing The gross weight meter of viscosity resin.

Binding agent the most according to claim 1, wherein said contact adhesive is optical clarity, described optical clarity The % absorbance of flame-retardant pressure-sensitive binding agent is at least 90%, and mist degree is less than 10%.

Binding agent the most according to claim 1, wherein said (methyl) acrylate group block copolymer includes (methyl) Acrylate diblock, three blocks or star block copolymer.

Binding agent the most according to claim 1, wherein said (methyl) acrylate group block copolymer includes three blocks Copolymer, described triblock copolymer comprises:

At least two A end-blocks polymer unit, described A end-blocks polymer unit is each derived from including (methyl) third First monoethylenically unsaturated monomer of olefin(e) acid ester, the glass transition temperature of the most each A end-blocks is at least 50 DEG C；With

At least one B mid block polymers unit, described B mid block polymers unit is derived from including (methyl) acrylic acid Ester or the second monoethylenically unsaturated monomer of vinyl esters, the glass transition temperature of the most each B mid-block is not more than 20 ℃；And at least one in wherein said first monoethylenically unsaturated monomer or described second monoethylenically unsaturated monomer includes (methyl) acrylate monomer.

Binding agent the most according to claim 4, wherein said (methyl) acrylate based triblock copolymer includes (poly-first Base acrylic acid methyl ester .)-(polyalkyl acrylate)-(polymethyl methacrylate) copolymer.

Binding agent the most according to claim 5, wherein said polyalkyl acrylate block constitutes polymer, described poly- Compound comprises at least one acrylate monomer, and described acrylate monomer has the alkyl group containing 1-20 carbon atom.

Binding agent the most according to claim 2, the % absorbance of the flame-retardant pressure-sensitive binding agent of wherein said optical clarity is At least 95%, and mist degree is less than 5%.

Binding agent the most according to claim 7, the flame-retardant pressure-sensitive binding agent of wherein said optical clarity have 0.16 to Yellowing factor b* in the range of 2.0.

Binding agent the most according to claim 1, wherein said flame-retardant pressure-sensitive binding agent passes through when being coated on backing Vertical combustion test FAR 25.853a, described backing comprises polyurethane or fluorothermoplasts.

Binding agent the most according to claim 1, the most halogen-containing wherein said flame-retardant additive includes phosphate ester.

11. 1 kinds of methods preparing binding agent, comprising:

(methyl) acrylate group block copolymer is provided；

Halogen-free flame-retardant is provided；And

At least one extra additive optionally provided；And

By (methyl) acrylate group block copolymer and described halogen-free flame-retardant and a kind of extra interpolation Agent is blended to form contact adhesive, and the most halogen-containing wherein said fire retardant accounts at least 10 weight % of binding agent, described extremely Few a kind of additive selected from tackifying resin, antioxidant, inorganic filler, ultra-violet stabilizer, plasticizer, softening agent or they Combination.

12. methods according to claim 11, wherein said contact adhesive is optical clarity, described optical clarity The % absorbance of flame-retardant pressure-sensitive binding agent is at least 90%, and mist degree is less than 10%.

13. methods according to claim 11, are wherein blended and include that hot melt is blended.

14. methods according to claim 13, wherein hot melt is blended and includes by described (methyl) acrylate-based block altogether Polymers and described halogen-free flame-retardant add to extruder the hot melt blend of extruding gained.

15. methods according to claim 11, wherein provide (methyl) acrylate group block copolymer to include providing molten In the solution of (methyl) acrylate group block copolymer of solvent, and be blended include solvent be blended.

16. methods according to claim 13, it also includes being coated on base material described contact adhesive hot melt.

17. methods according to claim 15, it also includes described contact adhesive solvent coating on base material.